US4741757A - Thiophenesulfonamides - Google Patents
Thiophenesulfonamides Download PDFInfo
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- US4741757A US4741757A US07/024,452 US2445287A US4741757A US 4741757 A US4741757 A US 4741757A US 2445287 A US2445287 A US 2445287A US 4741757 A US4741757 A US 4741757A
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/30—Hetero atoms other than halogen
- C07D333/34—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D521/00—Heterocyclic compounds containing unspecified hetero rings
Definitions
- This invention relates to novel compounds of the formula: ##STR1## wherein W is O or S;
- R is H or CH 3
- R 3 and R 4 are independently C 1 -C 3 alkyl
- R 3 and R 4 may be taken together as (CH 2 ) 4 , (CH 2 ) 5 or CH 2 CH 2 OCH 2 CH 2 ;
- R 5 is C 1 -C 3 alkyl or CH 2 CH ⁇ CH 2 ;
- R 7 is C 1 -C 3 alkyl
- R 8 is H, C 1 -C 3 alkyl or CH 2 CH ⁇ CH 2 ;
- R 9 is H or C 1 -C 3 alkyl
- R 10 is C 1 -C 2 alkyl
- n 0, 1 or 2;
- X is CH 3 , OCH 3 , OCH 2 CH 3 , CH 2 OCH 3 or OCF 2 H;
- Z is CH or N
- R 1 and the sulfonylurea bridge are on adjacent carbon atoms of the thiophene ring and also provided that when X is OCF 2 H then Z is CH.
- W is O
- R is H
- R 1 is H, C 1 -C 2 alkyl, CF ⁇ CFCF 3 , Cl, Br, SO 2 N(CH 3 ) 2 , SO 2 (C 1 -C 2 alkyl) or CO 2 (C 1 -C 2 alkyl);
- X is CH 3 or OCH 3 .
- the compounds of Formula I can be prepared in an inert organic solvent by one of several processes.
- the compounds of Formula I are produced by reacting a sulfonamide of Formula II, wherein R 1 and R 2 are as previously defined, and an N-pyrimidinyl- or N-triazinylcarbamate of Formula III, wherein W, X and Z have the meanings defined under Formula I, and B--O-- is a phenoxy or alkoxy group which can be displaced as illustrated in Equation (1).
- a sulfonamide of Formula II wherein R 1 and R 2 are as previously defined
- an N-pyrimidinyl- or N-triazinylcarbamate of Formula III wherein W, X and Z have the meanings defined under Formula I
- B--O-- is a phenoxy or alkoxy group which can be displaced as illustrated in Equation (1).
- compounds of Formula I are produced by reacting a sulfonyl isocyanate or sulfonyl isothiocyanate of Formula IV, wherein R 1 , R 2 and W are as previously defined, in the presence or absence of a base, with an amine of Formula V, wherein R, X and Z have the meanings defined under Formula I, illustrated in Equation (2). ##STR3##
- compounds of Formula I can be prepared by reacting a sulfonamide of Formula II given above, in the presence or absence of a base, with an isocyanate or isothiocyanate of Formula VI wherein W, X and Z are as previously defined. ##STR4##
- compounds of Formula I can be produced by reacting an N-thiophenesulfonylcarbamate of Formula VII, illustrated in Equation (4), wherein R 1 , R 2 and B have the meanings defined above, with an amine of Formula V. ##STR5##
- cyclopropylpyrimidines and cyclopropyltriazines of Formula V to which the intermediates of Formulae III and VI are closely related, are also known and can be produced by one skilled in the art according to methods described in U.S. 4,515,626.
- Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts.
- Typical liquid diluents and solvents are described in Marsden, “Solvents Guide”, 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C.
- compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp. 147ff. and “Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
- the ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
- the ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter.
- the product is reblended before packaging.
- a slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
- the ingredients are blended, hammer-milled and then moistened with about 12% water.
- the mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings).
- the granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.
- the ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns.
- the resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
- the ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended an sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
- the ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
- the salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
- the active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
- the ingredients are blended and milled to pass through a 100 mesh screen.
- This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material.
- the fluidization and spraying are continued until granules of the desired size range are made.
- the spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%.
- the material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
- the ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening).
- the concentrate may be formulated further if necessary.
- the ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns.
- the material is sifted through a U.S.S. No. 50 screen and then packaged.
- the ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size.
- the material is reblended and then packaged.
- the ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns.
- the product can be used directly, extended with oils, or emulsified in water.
- the active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns.
- the ground concentrate is then blended with powdered pyrophyllite until homogeneous.
- the ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
- the rates of application for the compounds of the invention are determined by a number of factors, including their use as plant growth regulants or as herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc.
- the subject compounds should be applied at levels of around 0.01 to 10 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required.
- the compounds of the invention may be used in combination with any other commercial herbicide; examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types.
- X axillary stimulation
- Two round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil.
- One pan was planted with blackgrass (Alopecurus myosuroides), sugar beets, nutsedge (Cyperus rotundus) tubers, crabgrass (Digitaria sanquinalis), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), giant foxtail (Setaria faberii) and rape (Brassica napus).
- blackgrass Alopecurus myosuroides
- sugar beets nutsedge (Cyperus rotundus) tubers
- crabgrass Digitaria sanquinalis
- sicklepod Cassia obtusifolia
- teaweed Sida spinosa
- jimsonweed Datura stramonium
- the other pan was planted with wheat, cotton, rice, corn, soybean, wild oats (Avena fatua), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense) and barnyardgrass (Echinochloa crusgalli).
- wild oats Avena fatua
- cocklebur Xanthium pensylvanicum
- morningglory Ipomoea hederacea
- johnsongrass Sorghum halepense
- barnyardgrass Echinochloa crusgalli
- Two round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil.
- One pan was planted with blackgrass, sugar beets, nutsedge, crabgrass, sicklepod, teaweed, jimsonweed, velvetleaf, giant foxtail and rape.
- the other pan was planted with wheat, cotton, rice, corn, soybeans, wild oats, cocklebur, morningglory, johnsongrass, and barnyardgrass.
- the two pans were sprayed preemergence with the chemicals dissolved in a nonphytotoxic solvent.
- Treated plants and controls were maintained in the greenhouse for 28 days, then all treated plants were compared to controls and visually rated for plant response.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Plural Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Thiophenesulfonamides useful as herbicides and plant growth regulants, herbicidal compositions containing thiophenesulfonamides, and methods of applying the compositions to areas containing undesired vegetation are described.
Description
This application is a divisional of copending application U.S. Ser. No. 849,332 filed Apr. 10, 1986, now U.S. Pat. No. 4,668,281, which is a continuation-in-part of U.S. Ser. No. 735,529 filled May 20, 1985, now abandoned.
This invention relates to novel compounds of the formula: ##STR1## wherein W is O or S;
R is H or CH3
R1 is H, C1 -C4 alkyl, CH2 CH═CH2, CF═CFCF3, C1 -C2 alkoxy, NO2, Cl, Br, SO2 NR3 R4, SO2 N(OCH3)CH3, S(O)n R5, CO2 R6, C(O)NR7 R8, C(O)R9 or C1 -C2 alkyl substituted with F, Cl, C1 -C2 alkoxy, C1 -C2 alkylthio or CN;
R2 is H, Cl, F, Br, C1 -C2 alkyl, C1 -C2 alkoxy, S(O)n R10, C1 -C2 haloalkyl, CN, C2 -C3 cyanoalkyl, CH2 OCH3, CH2 SCH3 or CH2 CH2 OCH3 ;
R3 and R4 are independently C1 -C3 alkyl;
R3 and R4 may be taken together as (CH2)4, (CH2)5 or CH2 CH2 OCH2 CH2 ;
R5 is C1 -C3 alkyl or CH2 CH═CH2 ;
R6 is C1 -C3 alkyl, CH2 CH═CH2, CH2 C.tbd.CH, CH2 CH2 Cl or CH2 CH2 OCH3 ;
R7 is C1 -C3 alkyl;
R8 is H, C1 -C3 alkyl or CH2 CH═CH2 ;
R9 is H or C1 -C3 alkyl;
R10 is C1 -C2 alkyl;
n is 0, 1 or 2;
X is CH3, OCH3, OCH2 CH3, CH2 OCH3 or OCF2 H; and
Z is CH or N;
and their agriculturally suitable salts; provided that R1 and the sulfonylurea bridge are on adjacent carbon atoms of the thiophene ring and also provided that when X is OCF2 H then Z is CH.
Preferred for reasons of their higher herbicidal activity, greater plant growth regulant activity or more favorable ease of synthesis are:
(1) Compounds of Formula I wherein
W is O;
R is H;
R1 is H, C1 -C2 alkyl, CF═CFCF3, Cl, Br, SO2 N(CH3)2, SO2 (C1 -C2 alkyl) or CO2 (C1 -C2 alkyl);
R2 is H, F, Br, Cl, CH3, S(O)n CH3, or CH2 OCH3 ; and
X is CH3 or OCH3.
Specifically Preferred for reasons of greatest ease of synthesis and/or greatest herbicidal efficacy is:
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic acid, methyl ester.
The compounds of Formula I can be prepared in an inert organic solvent by one of several processes.
According to one process, the compounds of Formula I are produced by reacting a sulfonamide of Formula II, wherein R1 and R2 are as previously defined, and an N-pyrimidinyl- or N-triazinylcarbamate of Formula III, wherein W, X and Z have the meanings defined under Formula I, and B--O-- is a phenoxy or alkoxy group which can be displaced as illustrated in Equation (1). ##STR2##
According to a second process, compounds of Formula I are produced by reacting a sulfonyl isocyanate or sulfonyl isothiocyanate of Formula IV, wherein R1, R2 and W are as previously defined, in the presence or absence of a base, with an amine of Formula V, wherein R, X and Z have the meanings defined under Formula I, illustrated in Equation (2). ##STR3##
According to a further process, illustrated in Equation (3), compounds of Formula I can be prepared by reacting a sulfonamide of Formula II given above, in the presence or absence of a base, with an isocyanate or isothiocyanate of Formula VI wherein W, X and Z are as previously defined. ##STR4##
Furthermore, compounds of Formula I can be produced by reacting an N-thiophenesulfonylcarbamate of Formula VII, illustrated in Equation (4), wherein R1, R2 and B have the meanings defined above, with an amine of Formula V. ##STR5##
The resulting ureas of Formula I can, if required, be converted by means of amines, alkali metal hydroxides or alkaline-earth metal hydroxides or quaternary ammonium bases, into addition salts. This is effected, for example, by reaction with an equimolar amount of a base, and removal of the solvent by evaporation.
The starting materials of the Formulae II, IV and VII are, in many cases, known or can be prepared by one skilled in the art according to methods described in U.S. Pat. Nos. 4,127,405; 4,398,939; 4,481,910; and 4,481,029, the disclosures of which are incorporated herein by reference.
The cyclopropylpyrimidines and cyclopropyltriazines of Formula V, to which the intermediates of Formulae III and VI are closely related, are also known and can be produced by one skilled in the art according to methods described in U.S. 4,515,626.
The selection of the appropriate process for the production of compounds of Formula I is dependent in part on the relative reactivities and syntheses of compounds of Formulae II-VII. Such decisions are obvious to one skilled in the art.
The following Example sets forth the invention in greater detail.
To 0.8 g of 2 -amino-4-cyclopropyl-6-methoxy-1,3,5-triazine in 35 mL of dry methylene chloride was added methyl 3-isocyanatosulfonylthiophene-2-carboxylate. After being stirred at reflux for one-half hour, the mixtue was cooled in an ice-acetone bath and the precipitate removed by filtration. Evaporation of the filtrate yielded a residue which was washed with a small amount of acetonitrile to yield 0.3 g of a solid. This product, m.p. 142°-169° C., showed absorption peaks by infrared spectroscopy at 1730, 1720, 1600 and 1550 cm-1, consistent with the desired structure.
NMR (CDCl3): δ 3.85 (s, CH3 O on triazine) 4.05 (s, CH3 O ester) 0.8-1.5 (m, cyclopropyl) 7.7-7.9 (m, thiophene).
This product was sufficiently pure for the purposes of this invention.
Following the procedures described earlier and exemplified in the Example, one skilled in the art can prepare the compounds of Tables I, II and III. ##STR6##
TABLE I
______________________________________
General Structure I
m.p.
RR.sub.1 R.sub.2 W XZ (°C.)
______________________________________
HHH OCH.sub.3 CH
HHH OOCH.sub.3 CH
HHH OCH.sub.3 N
HHH OOCH.sub.3 N
HClH OCH.sub.3 CH
HClH OOCH.sub.3 CH
HClH OCH.sub.3 N
HClH OOCH.sub.3 N
HBrH OCH.sub.3 CH
HBrH OOCH.sub.3 CH
HBrH OCH.sub.3 N
HBrH OOCH.sub.3 N
HCH.sub.3 H OCH.sub.3 CH
HCH.sub.3 H OOCH.sub.3 CH
HCH.sub.3 H OCH.sub.3 N
HCH.sub.3 H OOCH.sub.3 N
HCH.sub.2 CH.sub.3 H OCH.sub.3 CH
HCH.sub.2 CH.sub.3 H OOCH.sub.3 CH
HCH.sub.2 CH.sub.3 H OCH.sub.3 N
HCH.sub.2 CH.sub.3 H OOCH.sub.3 N
CH.sub.3 CH.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 CH
HCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 5-Cl
OOCH.sub.3 CH
HCH.sub.2 CHCH.sub.2 H
SCH.sub.3 N
HCFCFCF.sub.3 H OCH.sub.3 CH
HCFCFCF.sub.3 H OOCH.sub.3 CH
HCFCFCF.sub.3 H OCH.sub.3 N
HCFCFCF.sub.3 H OOCH.sub.3 N
HOCH.sub.3 H OOCH.sub.2 CH.sub.3 N
HOCH.sub.2 CH.sub.3 H
OCH.sub.2 OCH.sub.3 CH
HNO.sub.2 H OOCF.sub.2 HCH
HSO.sub.2 N(CH.sub.3).sub.2 H
OCH.sub.3 CH
HSO.sub.2 N(CH.sub.3).sub.2 H
OOCH.sub.3 CH
HSO.sub.2 N(CH.sub.3).sub.2 H
OCH.sub.3 N
HSO.sub.2 N(CH.sub.3).sub.2 H
OOCH.sub.3 N
HSO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.3)5-CH.sub.3
OCH.sub.3 CH
HSO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.2 CH.sub.3)H
OOCH.sub.3 CH
HSO.sub.2 N(CH.sub.2 CH.sub.3).sub.2 H
OCH.sub.3 N
HSO.sub.2 N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2 H
OOCH.sub.3 N
HSO.sub.2 N(OCH.sub.3)CH.sub.3 H
OCH.sub.3 CH
HSCH.sub.3 H OOCH.sub.3 CH
HSCH.sub.2 CH.sub.3 H
OCH.sub.3 N
HSCH.sub.2 CH.sub.2 CH.sub.3 H
OOCH.sub.3 N
HSCH.sub.2 CHCH.sub.2 H
OCH.sub.3 CH
HS(O)CH.sub.3 4-Cl OOCH.sub.3 CH
HS(O)CH.sub.2 CH.sub.3 H
OCH.sub.3 N
HS(O)CH.sub.2 CH.sub.2 CH.sub.3 H
OOCH.sub.3 N
HS(O)CH.sub.2 CHCH.sub.2 H
OCH.sub.3 CH
HSO.sub.2 CH.sub.3 H OCH.sub.3 CH
HSO.sub.2 CH.sub.3 H OOCH.sub.3 CH
HSO.sub. 2 CH.sub.3 H
OCH.sub.3 N
HSO.sub.2 CH.sub.3 H OOCH.sub.3 N
HSO.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 CH
HSO.sub.2 CH.sub.2 CH.sub.3 H
OOCH.sub.3 CH
HSO.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 N
HSO.sub.2 CH.sub.2 CH.sub.3 H
OOCH.sub.3 N
HSO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 CH
HSO.sub.2 CH.sub.2 CHCH.sub.2 H
OOCH.sub.3 CH
HCO.sub.2 CH.sub.3 H OCH.sub.3 CH
HCO.sub.2 CH.sub.3 H OOCH.sub.3 CH
HCO.sub.2 CH.sub.3 H OCH.sub.3 N
HCO.sub.2 CH.sub.3 H OOCH.sub.3 N
HCO.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 CH
HCO.sub.2 CH.sub.2 CH.sub.3 H
OOCH.sub.3 CH
HCO.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 N
H CO.sub.2 CH.sub.2 CH.sub.3 H
OOCH.sub.3 N
HCO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 CH
HCO.sub.2 CH(CH.sub.3).sub.2 4-CH.sub.3
OOCH.sub.3 CH
HCO.sub.2 CH.sub.2 CHCH.sub.2 H
OCH.sub.3 N
HCO.sub.2 CH.sub.2 CCHH
OOCH.sub.3 N
HCO.sub.2 CH.sub.2 CH.sub.2 ClH
OCH.sub.3 CH
HCO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H
OOCH.sub.3 CH
HCONHCH.sub.3 H OCH.sub.3 N
HCON(CH.sub.3)CH.sub.2 CH.sub.3 H
OOCH.sub.3 N
HCON(CH.sub.2 CH.sub.3).sub.2 H
OCH.sub.3 CH
HCON(CH.sub.2 CH.sub.2 CH.sub.3)(CH.sub.3)H
OOCH.sub.3 CH
HCON(CH.sub.2 CHCH.sub.2)(CH.sub.3) H
OCH.sub.3 N
HCHOH OOCH.sub.3 N
HC(O)CH.sub.3 H OCH.sub.3 CH
HC(O)CH.sub. 2 CH.sub.3 H
OOCH.sub.3 N
HC(O)CH.sub.2 CH.sub.2 CH.sub.3 H
OCH.sub.3 CH
HCF.sub.2 HH OOCH.sub.3 CH
HCH.sub.2 CH.sub.2 FH
OCH.sub.3 N
HCCl.sub.3 H OOCH.sub.3 N
HCHClCH.sub.2 ClH OCH.sub.3 CH
HCH.sub.2 OCH.sub.3 H
OOCH.sub.3 CH
HCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 H
OCH.sub.3 N
HCH.sub.2 SCH.sub.2 CH.sub.3 H
OOCH.sub.3 N
HCH.sub.2 CH.sub.2 SCH.sub.3 H
OCH.sub.3 CH
HCH.sub.2 CNH OOCH.sub.3 CH
HCH.sub.2 CH.sub.2 CNH
OCH.sub.3 N
OCH.sub.3 CH
##STR7## OOCH.sub.3 CH
##STR8## OCH.sub.3 N
##STR9## OOCH.sub.3 N
##STR10## OCH.sub.3 CH
##STR11## OOCH.sub.3 CH
##STR12## OCH.sub.3 N
##STR13## OOCH.sub.3 N
##STR14## OCH.sub.3 CH
##STR15## OOCH.sub.3 CH
##STR16## OCH.sub.3 N
##STR17## OOCH.sub.3 N
HCO.sub.2 CH.sub.3 H OOCH.sub.2 CH.sub.3 CH
HCO.sub.2 CH.sub.3 H OCH.sub.2 OCH.sub.3 CH
HCO.sub.2 CH.sub.3 H OOCF.sub.2 HCH
HCO.sub.2 CH.sub.3 H OOCH.sub.2 CH.sub.3 N
HCO.sub.2 CH.sub.3 H OCH.sub.2 OCH.sub.3 N
HCO.sub.2 CH.sub.3 5-CH.sub.3
OCH.sub.3 CH
HCO.sub.2 CH.sub.3 5-CH.sub.3
OOCH.sub.3 CH
HCO.sub.2 CH.sub.3 5-CH.sub.3
OCH.sub.3 N
HCO.sub.2 CH.sub.3 5-CH.sub.3
OOCH.sub.3 N
##STR18## OCH.sub.3 CH
##STR19## OOCH.sub.3 CH
##STR20## OCH.sub.3 N
##STR21## OOCH.sub.3 N
##STR22## OCH.sub.3 CH
##STR23## OOCH.sub.3 CH
##STR24## OCH.sub.3 N
##STR25## OOCH.sub.3 N
##STR26## OCH.sub.3 CH
##STR27## OOCH.sub.3 CH
##STR28## OCH.sub.3 N
##STR29## OOCH.sub.3 N
HCO.sub.2 CH.sub.3 H OOCH.sub.2 CH.sub.3 CH
HCO.sub.2 CH.sub.3 H OCH.sub.2 OCH.sub.3 CH
HCO.sub.2 CH.sub.3 H OOCF.sub.2 HCH
HCO.sub.2 CH.sub.3 H OOCH.sub.2 CH.sub.3 N
HCO.sub.2 CH.sub.3 H OCH.sub.2 OCH.sub.3 N
HCO.sub.2 CH.sub.3 4-CH.sub.3
OCH.sub.3 CH
HCO.sub.2 CH.sub.3 4-CH.sub.3
OOCH.sub.3 CH
HCO.sub.2 CH.sub.3 4-CH.sub.3
OCH.sub.3 N
HCO.sub.2 CH.sub.3 4-CH.sub.3
OOCH.sub.3 N
HCO.sub.2 CH.sub.3 4-Br
OOCH.sub.3 N
HCO.sub.2 CH.sub.3 4-Br
OCH.sub.3 N
HCO.sub.2 CH.sub.3 4-Br
OOCH.sub.3 CH
HCO.sub.2 CH.sub.3 4-Br
OCH.sub.3 CH
______________________________________
TABLE II
__________________________________________________________________________
General Structure II
R R.sub.1 R.sub.2
W X Z m.p. (°C.)
__________________________________________________________________________
H H H O CH.sub.3
CH
H H H O OCH.sub.3
CH
H H H O CH.sub.3
N
H H H O OCH.sub.3
N
H Cl H O CH.sub.3
CH
H Cl H O OCH.sub.3
CH
H Cl H O CH.sub.3
N
H Cl H O OCH.sub.3
N
H Br H O CH.sub.3
CH
H Br H O OCH.sub.3
CH
H Br H O CH.sub.3
N
H Br H O OCH.sub.3
N
H CH.sub.3 H O CH.sub.3
CH
H CH.sub.3 H O OCH.sub.3
CH
H CH.sub.3 H O CH.sub.3
N
H CH.sub.3 H O OCH.sub.3
N
H CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CH.sub.2 CH.sub.3
H O OCH.sub.3
CH
H CH.sub.2 CH.sub.3
H O CH.sub.3
N
H CH.sub.2 CH.sub.3
H O OCH.sub.3
N
CH.sub.3
CH.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3
5-Cl
O OCH.sub.3
CH
H CH.sub.2 CHCH.sub.2
H S CH.sub.3
N
H CFCFCF.sub.3 H O CH.sub.3
CH
H CFCFCF.sub.3 H O OCH.sub.3
CH
H CFCFCF.sub.3 H O CH.sub.3
N
H CFCFCF.sub.3 H O OCH.sub.3
N
H OCH.sub.3 H O OCH.sub.2 CH.sub.3
N
H OCH.sub.2 CH.sub.3
H O CH.sub.2 OCH.sub.3
CH
H NO.sub.2 H O OCF.sub.2 H
CH
H SO.sub.2 N(CH.sub.3).sub.2
H O CH.sub.3
CH
H SO.sub.2 N(CH.sub.3).sub.2
H O OCH.sub.3
CH
H SO.sub.2 N(CH.sub.3).sub.2
H O CH.sub.3
N
H SO.sub.2 N(CH.sub.3).sub.2
H O OCH.sub.3
N
H SO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.3)
5-CH.sub.3
O CH.sub.3
CH
H SO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.2 CH.sub.3)
H O OCH.sub.3
CH
H SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2
H O CH.sub.3
N
H SO.sub.2 N(CH.sub.2 CH.sub.2 CH.sub.3 ).sub.2
H O OCH.sub.3
N
H SO.sub.2 N(OCH.sub.3)CH.sub.3
H O CH.sub.3
CH
H SCH.sub.3 H O OCH.sub.3
CH
H SCH.sub.2 CH.sub.3
H O CH.sub.3
N
H SCH.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H SCH.sub.2 CHCH.sub.2
H O CH.sub.3
CH
H S(O)CH.sub.3 4-Cl
O OCH.sub.3
CH
H S(O)CH.sub.2 CH.sub.3
H O CH.sub.3
N
H S(O)CH.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H S(O)CH.sub.2 CHCH.sub.2
H O CH.sub.3
CH
H SO.sub.2 CH.sub.3
H O CH.sub.3
CH
H SO.sub.2 CH.sub.3
H O OCH.sub.3
CH
H SO.sub.2 CH.sub.3
H O CH.sub.3
N
H SO.sub.2 CH.sub.3
H O OCH.sub.3
N
H SO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H SO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
CH
H SO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
N
H SO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H SO.sub.2 CH.sub.2 CHCH.sub.2
H O OCH.sub.3
CH
H CO.sub.2 CH.sub.3
H O CH.sub.3
CH
H CO.sub.2 CH.sub.3
H O OCH.sub.3
CH
H CO.sub.2 CH.sub.3
H O CH.sub.3
N
H CO.sub.2 CH.sub.3
H O OCH.sub.3
N 142-169
H CO.sub.2 CH.sub.3
4-CH.sub.3
O OCH.sub.3
N 177-179(d)
H CO.sub.2 CH.sub.3
4-CH.sub.3
O CH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH 60-62
H CO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
CH
H CO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CO.sub.2 CH(CH.sub.3).sub.2
4-CH.sub.3
O OCH.sub.3
CH
H CO.sub.2 CH.sub.2 CHCH.sub.2
H O CH.sub.3
N
H CO.sub.2 CH.sub.2 CCH
H O OCH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.2 Cl
H O CH.sub.3
CH
H CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3
H O OCH.sub.3
CH
H CONHCH.sub.3 H O CH.sub.3
N
H CON(CH.sub.3)CH.sub.2 CH.sub.3
H O OCH.sub.3
N 134-136
H CON(CH.sub.2 CH.sub.3).sub.2
H O CH.sub.3
CH
H CON(CH.sub.2 CH.sub.2 CH.sub.3)(CH.sub.3)
H O OCH.sub.3
CH
H CON(CH.sub.2 CHCH.sub.2)(CH.sub.3)
H O CH.sub.3
N
H CHO H O OCH.sub.3
N
H C(O)CH.sub.3 H O CH.sub.3
CH
H C(O)CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H C(O)CH.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CF.sub.2 H H O OCH.sub.3
CH
H CH.sub.2 CH.sub.2 F
H O CH.sub.3
N
H CCl.sub.3 H O OCH.sub.3
N
H CHClCH.sub.2 Cl
H O CH.sub.3
CH
H CH.sub.2 OCH.sub.3
H O OCH.sub.3
CH
H CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3
H O CH.sub.3
N
H CH.sub.2 SCH.sub.2 CH.sub.3
H O OCH.sub.3
N
H CH.sub.2 CH.sub.2 SCH.sub.3
H O CH.sub.3
CH
H CH.sub.2 CN H O OCH.sub.3
CH
H CH.sub.2 CH.sub.2 CN
H O CH.sub.3
N
##STR30## H O CH.sub.3
CH
H
##STR31## H O OCH.sub.3
CH
H
##STR32## H O CH.sub.3
N
H
##STR33## H O OCH.sub.3
N 167-169
H
##STR34## H O CH.sub.3
CH
H
##STR35## H O OCH.sub.3
CH
H
##STR36## H O CH.sub.3
N
H
##STR37## H O OCH.sub.3
N
H
##STR38## H O CH.sub.3
CH
H
##STR39## H O OCH.sub.3
CH
H
##STR40## H O CH.sub.3
N
H
##STR41## H O OCH.sub.3
N
H CO.sub.2 CH.sub.3
H O OCH.sub.2 CH.sub.3
CH
H CO.sub.2 CH.sub.3
H O CH.sub.2 OCH.sub.3
CH
H CO.sub.2 CH.sub.3
H O OCF.sub.2 H
CH
H CO.sub.2 CH.sub.3
H O OCH.sub.2 CH.sub.3
N
H CO.sub.2 CH.sub.3
H O CH.sub.2 OCH.sub.3
N
H CO.sub.2 CH.sub.3
4-CH.sub.3
O CH.sub.3
CH
H CO.sub.2 CH.sub.3
4-CH.sub.3
O OCH.sub.3
CH
H CO.sub.2 CH.sub.3
4-CH.sub.3
O CH.sub.3
N
H CO.sub.2 CH.sub.3
4-CH.sub.3
O OCH.sub.3
N 177-179(d)
H CO.sub.2 CH.sub.3
4-Br
O CH.sub.3
N
H CO.sub.2 CH.sub.3
4-Br
O OCH.sub.3
N 88-95
H CO.sub.2 CH.sub.3
4-Br
O CH.sub.3
CH
H CO.sub.2 CH.sub.3
4-Br
O OCH.sub.3
CH
__________________________________________________________________________
TABLE III
__________________________________________________________________________
General Structure III
m.p.
R R.sub.1 R.sub.2
W X Z (°C.)
__________________________________________________________________________
H H H O CH.sub.3
CH
H H H O OCH.sub.3
CH
H H H O CH.sub.3
N
H H H O OCH.sub.3
N
H Cl H O CH.sub.3
CH
H Cl H O OCH.sub.3
CH
H Cl H O CH.sub.3
N
H Cl H O OCH.sub.3
N
H Br H O CH.sub.3
CH
H Br H O OCH.sub.3
CH
H Br H O CH.sub.3
N
H Br H O OCH.sub.3
N
H CH.sub.3 H O CH.sub.3
CH
H CH.sub.3 H O OCH.sub.3
CH
H CH.sub.3 H O CH.sub.3
N
H CH.sub.3 H O OCH.sub.3
N
H CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CH.sub.2 CH.sub.3
H O OCH.sub.3
CH
H CH.sub.2 CH.sub.3
H O CH.sub.3
N
H CH.sub.2 CH.sub.3
H O OCH.sub.3
N
CH.sub.3
CH.sub.2 CH.sub. 2 CH.sub.3
H O CH.sub.3
CH
H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3
5-Cl O OCH.sub.3
CH
H CH.sub.2 CH═CH.sub.2
H S CH.sub.3
N
H CF═CFCF.sub.3
H O CH.sub.3
CH
H CF═CFCF.sub.3
H O OCH.sub.3
CH
H CF═CFCF.sub.3
H O CH.sub.3
N
H CF═CFCF.sub.3
H O OCH.sub.3
N
H OCH.sub.3 H O OCH.sub.2 CH.sub.3
N
H OCH.sub.2 CH.sub.3
H O CH.sub.2 OCH.sub.3
CH
H NO.sub.2 H O OCF.sub.2 H
CH
H SO.sub.2 N(CH.sub.3).sub.2
H O CH.sub.3
CH
H SO.sub.2 N(CH.sub.3).sub.2
H O OCH.sub.3
CH
H SO.sub.2 N(CH.sub.3).sub.2
H O CH.sub.3
N
H SO.sub.2 N(CH.sub.3).sub.2
H O OCH.sub.3
N
H SO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.3)
5-CH.sub.3
O CH.sub.3
CH
H SO.sub.2 N(CH.sub.3)(CH.sub.2 CH.sub.2 CH.sub.3)
H O OCH.sub.3
CH
H SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2
H O CH.sub.3
N
H SO.sub.2 N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2
H O OCH.sub.3
N
H SO.sub.2 N(OCH.sub.3)CH.sub.3
H O CH.sub.3
CH
H SCH.sub.3 H O OCH.sub.3
CH
H SCH.sub.2 CH.sub.3
H O CH.sub.3
N
H SCH.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H SCH.sub.2 CH═CH.sub.2
H O CH.sub.3
CH
H S(O)CH.sub.3 2-Cl O OCH.sub.3
CH
H S(O)CH.sub.2 CH.sub.3
H O CH.sub.3
N
H S(O)CH.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H S(O)CH.sub.2 CH═CH.sub.2
H O CH.sub.3
CH
H SO.sub.2 CH.sub.3
H O CH.sub.3
CH
H SO.sub.2 CH.sub.3
H O OCH.sub.3
CH
H SO.sub.2 CH.sub.3
H O CH.sub.3
N
H SO.sub.2 CH.sub.3
H O OCH.sub.3
N
H SO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H SO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
CH
H SO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
N
H SO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H SO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H SO.sub.2 CH.sub.2 CH═CH.sub.2
H O OCH.sub.3
CH
H CO.sub.2 CH.sub.3
H O CH.sub.3
CH
H CO.sub.2 CH.sub.3
H O OCH.sub.3
CH
H CO.sub.2 CH.sub.3
H O CH.sub.3
N
H CO.sub.2 CH.sub.3
H O OCH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
CH
H CO.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CO.sub.2 CH(CH.sub.3).sub.2
2-CH.sub.3
O OCH.sub.3
CH
H CO.sub.2 CH.sub.2 CH═CH.sub.2
H O CH.sub.3
N
H CO.sub.2 CH.sub.2 C.tbd.CH
H O OCH.sub.3
N
H CO.sub.2 CH.sub.2 CH.sub.2 Cl
H O CH.sub.3
CH
H CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3
H O OCH.sub.3
CH
H CONHCH.sub.3 H O CH.sub.3
N
H CON(CH.sub.3)CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H CON(CH.sub.2 CH.sub.3).sub.2
H O CH.sub.3
CH
H CON(CH.sub.2 CH.sub.2 CH.sub.3)(CH.sub.3)
H O OCH.sub.3
CH
H CON(CH.sub.2 CH═CH.sub.2)(CH.sub.3)
H O CH.sub.3
N
H CHO H O OCH.sub.3
N
H C(O)CH.sub.3 H O CH.sub.3
CH
H C(O)CH.sub.2 CH.sub.3
H O OCH.sub.3
N
H C(O)CH.sub.2 CH.sub.2 CH.sub.3
H O CH.sub.3
CH
H CF.sub.2 H H O OCH.sub.3
CH
H CH.sub.2 CH.sub.2 F
H O CH.sub.3
N
H CCl.sub.3 H O OCH.sub.3
N
H CHClCH.sub.2 Cl
H O CH.sub.3
CH
H CH.sub.2 OCH.sub.3
H O OCH.sub.3
CH
H CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3
H O CH.sub.3
N
H CH.sub.2 SCH.sub.2 CH.sub.3
H O OCH.sub.3
N
H CH.sub.2 CH.sub.2 SCH.sub.3
H O CH.sub.3
CH
H CH.sub.2 CN H O OCH.sub.3
CH
H CH.sub.2 CH.sub.2 CN
H O CH.sub.3
N
__________________________________________________________________________
Useful formulations of the compounds of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 1% to 99.9% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the following approximate proportions:
TABLE IV
______________________________________
Active Weight Percent*
Ingredient
Diluent(s)
Surfactant(s)
______________________________________
Wettable Powders
20-90 0-74 1-10
Oil Suspensions,
3-50 40-95 0-15
Emulsions, Solutions,
(including Emulsifiable
Concentrates)
Aqueous Suspension
10-50 40-84 1-20
Dusts 1-25 70-99 0-5
Granules and Pellets
0.1-95 5-99.9 0-15
High Strength 90-99 0-10 0-2
Compositions
______________________________________
*Active ingredient plus at least one of a Surfactant or a Diluent equals
100 weight percent.
Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J., but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide", 2nd Ed., Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, etc.
The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E. Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41;
R. W. Luckenbaugh, U.S. Pat. No. 3,309,192 Mar. 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;
G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96; and
J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
80%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
sodium alkylnaphthalenesulfonate
2%
sodium ligninsulfonate 2%
synthetic amorphous silica 3%
kaolinite 13%
______________________________________
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, reblended, and packaged.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
50%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
sodium alkylnaphthalenesulfonate
2%
low viscosity methyl cellulose
2%
diatomaceous earth 46%
______________________________________
The ingredients are blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.
______________________________________
Wettable Powder of Example 3
5%
attapulgite granules 95%
(U.S.S. 20-40 mesh; 0.84-0.42 mm)
______________________________________
A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
25%
aminocarbonyl]aminosulfonyl)]-2-thiophenecarboxylic
acid, methyl ester
anhydrous sodium sulfate 10%
crude calcium ligninsulfonate
5%
sodium alkylnaphthalenesulfonate
1%
calcium/magnesium bentonite 59%
______________________________________
The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings) may be packaged for use and the fines recycled.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
25%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
polyoxyethylene sorbitol hexaoleate
5%
highly aliphatic hydrocarbon oil
70%
______________________________________
The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
20%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
sodium alkylnaphthalenesulfonate
4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose
3%
attapulgite 69%
______________________________________
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essentially all below 100 microns, the material is reblended an sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
1%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
N,N--dimethylformamide 9%
attapulgite granules 90%
(U.S.S. 20-40 sieve)
______________________________________
The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
40%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
polyacrylic acid thickener 0.3%
dodecylphenol polyethylene glycol ether
0.5%
disodium phosphate 1%
monosodium phosphate 0.5%
polyvinyl alcohol 1.0%
water 56.7%
______________________________________
The ingredients are blended and ground together in a sand mill to produce particles essentially all under 5 microns in size.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
5%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester, ammonium salt
water 95%
______________________________________
The salt is added directly to the water with stirring to produce the solution, which may then be packaged for use.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
0.1%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
attapulgite granules 99.9%
(U.S.S. 20-40 mesh)
______________________________________
The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evaporate the solvent. The material is allowed to cool and then packaged.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3.5-triazin-2-yl)-
80%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
wetting agent 1%
crude ligninsulfonate salt (containing
10%
5-20% of the natural sugars)
attapulgite clay 9%
______________________________________
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
99%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
silica aerogel 0.5%
synthetic amorphous silica 0.5%
______________________________________
The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
90%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
dioctyl sodium sulfosuccinate
0.1%
synthetic fine silica 9.9%
______________________________________
The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S. No. 50 screen and then packaged.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
40%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
sodium ligninsulfonate 20%
montmorillonite clay 40%
______________________________________
The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material is reblended and then packaged.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
35%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
blend of polyalcohol carboxylic
6%
esters and oil soluble petroleum
sulfonates
xylene 59%
______________________________________
The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used directly, extended with oils, or emulsified in water.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
10%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
attapulgite 10%
Prophyllite 80%
______________________________________
The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.
______________________________________
3-[[(4-cyclopropane-6-methoxy-1,3,5-triazin-2-yl)-
10%
aminocarbonyl]aminosulfonyl]-2-thiophenecarboxylic
acid, methyl ester
chlorobenzene 84%
sorbitan monostearate and polyoxyethylene
6%
condensates thereof
______________________________________
The ingredients are combined and stirred to produce a solution which can be emulsified in water for application.
Test results indicate that the compounds of the present invention are highly active preemergent or postemergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad structures. Some of the compounds have utility for selective weed control in crops, such as rice and wheat. Alternatively, the subject compounds are useful to modify plant growth.
The rates of application for the compounds of the invention are determined by a number of factors, including their use as plant growth regulants or as herbicides, the crop species involved, the types of weeds to be controlled, weather and climate, formulations selected, mode of application, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.01 to 10 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, for plant growth modification or for situations where only short-term persistence is required.
The compounds of the invention may be used in combination with any other commercial herbicide; examples of which are those of the triazine, triazole, uracil, urea, amide, diphenylether, carbamate and bipyridylium types.
The herbicidal properties of the subject compounds were discovered in a number of greenhouse tests. The test procedures and results follow. ##STR42##
Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), morningglory (Ipomoea spp.), cocklebur (Xanthium pensylvanicum), sicklepod (Cassia obtusifolia). sorghum, corn, soybean, sugarbeet, cotton, rice, wheat and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with the test chemicals disslolved in a nonphytotoxic solvent. At the same time, these crop and weed species were treated with a soil/foliage application. At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The ratings, summarized in Table A, are based on a numerical scale extending from 0=no injury, to 10=complete kill. The accompanying descriptive symbols have the following meanings:
C=chlorosis or necrosis;
B=burn;
D=defoliation;
E=emergence inhibition;
G=growth retardation;
H=formative effects;
U=unusual pigmentation;
X=axillary stimulation;
S=albinism; and
6Y=abscised buds or flowers.
TABLE A
__________________________________________________________________________
Compound 1
Compound 2
Cmpd. 3
Cmpd. 4
Cmpd. 4
Cmpd. 5
Rate (kg/ha)
0.1 0.05
0.01
0.05 0.05 0.01 0.01
__________________________________________________________________________
POST-EMERGENCE
Morningglory
5C,9G 3C,9H
1H 4C,9G
10C 10C 3C,7G
Cocklebur
9C 2G 2G 5C,9G
9C 2C,8H
10C
Nutsedge
3G 3C,8G
2C,8G
3G 5G 0 0
Crabgrass
0 2G 0 0 0 0 0
Barnyardgrass
0 0 0 0 3C,8H
2C,5H
0
Wild Oats
0 0 0 0 3C,8G
3G 0
Wheat 0 0 0 0 9G 4G 0
Corn 3G 2C,6H
1C 2C,8H
2G 0 0
Soybean 3C,8G 2C 0 4G 5C,9G
4C,9H
0
Rice 0 2C 1C 4G 9G 4G 0
Sorghum 2G 2C,7H
1C,5G
2C,8H
3C,9H
7H 0
Sugar beets
9C 1C,6G
5G 3C,8G
9C 10C 9C
Cotton 4C,9G 2C,8H
2C,7G
3C,8G
10C 9G 10C
Cassia 0 -- -- -- -- -- --
Velvetleaf 4C,9G
1C,6G
2C,4G
10C 10C 10C
Giant Foxtail 5G 0 -- 3C,6G
2G 0
Cheatgrass 5G 0 0 2C,8G
0 0
Barley 0 0 -- 3C,9G
3C,7G
0
PRE-EMERGENCE
Morningglory
3C,9G 0 -- 2C,3H
9H 8G 0
Cocklebur
9H 5G -- 3C,4G
2C,6H
0 0
Nutsedge
3G 0 -- 3G 0 0 0
Crabgrass
0 0 -- 0 0 0 0
Barnyardgrass
0 0 -- 0 5H 0 0
Wild Oats
0 0 -- 0 5G 0 0
Wheat 0 0 -- 0 7G 0 0
Corn 7G 2C 3G 2C 0 0 0
Soybean 1C,3H 0 -- 1C 6H 2H 0
Rice 3G 0 -- 0 9H 6G 0
Sorghum 2G 2C 6H 2C,5G
3C,9H
2C,2G
0
Sugar beets
9C 1C 4G 3C,8G
4C,9G
8G 0
Cotton 9G 0 -- 0 7G 0 0
Cassia 4G -- -- -- -- -- --
Velvetleaf 1C 4G 2C,4G
2C,8H
0 0
Giant Foxtail 7G -- -- 8G 0 0
Cheatgrass 2G -- 0 6G 4G 0
Barley 0 -- -- 2C,5G
0 0
__________________________________________________________________________
Two round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with blackgrass (Alopecurus myosuroides), sugar beets, nutsedge (Cyperus rotundus) tubers, crabgrass (Digitaria sanquinalis), sicklepod (Cassia obtusifolia), teaweed (Sida spinosa), jimsonweed (Datura stramonium), velvetleaf (Abutilon theophrasti), giant foxtail (Setaria faberii) and rape (Brassica napus). The other pan was planted with wheat, cotton, rice, corn, soybean, wild oats (Avena fatua), cocklebur (Xanthium pensylvanicum), morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense) and barnyardgrass (Echinochloa crusgalli). The plants were grown for approximately fourteen days, then sprayed postemergence with the chemicals dissolved in a nonphytotoxic solvent.
Two round pans (25 cm diameter by 12.5 cm deep) were filled with Sassafras sandy loam soil. One pan was planted with blackgrass, sugar beets, nutsedge, crabgrass, sicklepod, teaweed, jimsonweed, velvetleaf, giant foxtail and rape. The other pan was planted with wheat, cotton, rice, corn, soybeans, wild oats, cocklebur, morningglory, johnsongrass, and barnyardgrass. The two pans were sprayed preemergence with the chemicals dissolved in a nonphytotoxic solvent.
Treated plants and controls were maintained in the greenhouse for 28 days, then all treated plants were compared to controls and visually rated for plant response.
Response ratings are based on a scale of 0 to 10: where 0=no effect, and 10=complete control. The type of response is indicated by letters where G=growth retardation and C=chlorosis/necrosis.
TABLE B
______________________________________
Compound 1
Rate (g/ha) 250 62 16 4
______________________________________
POST-EMERGENCE
Corn 2G 0 0 0
Wheat 0 0 0 0
Rice 3G 0 0 0
Soybean 3G 0 0 0
Cotton 10G 10G 7G 3G
Sugar beet 10C 10C 10C 10C
Crabgrass 3G 0 0 0
Johnsongrass 0 0 0 0
Blackgrass 3G 0 0 0
Barnyardgrass 0 0 0 0
Nutsedge 6C 3C 0 0
Giant Foxtail -- -- -- --
Wild Oats 0 0 0 0
Cocklebur 10G 10G 7G 4G
Morningglory 10G 9G 7G 3G
Teaweed 8G 5G 3G 0
Cassia 3G 0 0 0
Jimsonweed 9G 9G 4G 0
Velvetleaf 10G 10G 9G 4G
PRE-EMERGENCE
Corn 4G 2G 0 0
Wheat 0 0 0 0
Rice 8G 6G 4G 3G
Soybean 0 0 0 0
Cotton 7G 5G 2G 0
Sugar beet 9G 9G 6G 3G
Crabgrass 4G 3G 0 0
Johnsongrass 3G 0 0 0
Blackgrass 6G 4G 0 0
Barnyardgrass 0 0 0 0
Nutsedge 4G 0 0 0
Giant Foxtail 2G 0 0 0
Wild Oats 0 0 0 0
Cocklebur 7G 5G 3G 0
Morningglory 6G 2G 0 0
Teaweed 8G 6G 3G 0
Cassia 9G 7G 5G 3G
Jimsonweed 9G 8G 5G 0
Velvetleaf 9G 6G 3G 0
______________________________________
Claims (6)
1. A compound of the formula: ##STR43## wherein W is O or S;
R is H or CH3
R1 is H, C1 -C4 alkyl, CH2 CH═CH2, CF═CFCF3, C1 -C2 alkoxy, NO2, Cl, Br, SO2 NR3 R4, SO2 N(OCH3)CH3, S(O)n R5, CO2 R6, C(O)NR7 R8, C(O)R9 or C1 -C2 alkyl substituted with F, Cl, C1 -C2 alkoxy, C1 -C2 alkylthio or CN;
R2 is H, Cl, F, Br, C1 -C2 alkyl, C1 -C2 alkoxy, S(O)n R10, C1 -C2 haloalkyl, CN, C2 -C3 cyanoalkyl, CH2 OCH3, CH2 SCH3 or CH2 CH2 OCH3 ;
R3 and R4 are independently C1 -C3 alkyl;
R3 and R4 may be taken together as (CH2)4, (CH2)5 or CH2 CH2 OCH2 CH2 ;
R5 is C1 -C3 alkyl or CH2 CH═CH2 ;
R6 is C1 -C3 alkyl, CH2 CH═CH2, CH2 C.tbd.CH, CH2 CH2 Cl or CH2 CH2 OCH3 ;
R7 is C1 -C3 alkyl;
R8 is H, C1 -C3 alkyl or CH2 CH═CH2 ;
R9 is H or C1 -C3 alkyl;
R10 is C1 -C2 alkyl;
n is 0, 1 or 2;
X is CH3, OCH3, OCH2 CH3, CH2 OCH3 or OCF2 H; and
Z is CH;
and their agriculturally suitable salts; provided that R1 and the sulfonylurea bridge are on adjacent carbon atoms of the thiophene ring and also provided that when X is OCF2 H then Z is CH.
2. A compound according to claim 1 where
W is O;
R is H;
R1 is H, C1 -C2 alkyl, CF═CFCF3, Cl, Br, SO2 N(CH3)2, SO2 (C1 -C2 alkyl) or CO2 (C1 -C2 alkyl);
R2 is H, F, Br, Cl, CH3, S(O)n CH3, or CH2 OCH3 ; and
X is CH3 or OCH3.
3. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
4. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
5. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim 1.
6. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/024,452 US4741757A (en) | 1986-04-10 | 1987-03-11 | Thiophenesulfonamides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/849,332 US4668281A (en) | 1985-05-20 | 1986-04-10 | Thiophenesulfonamides |
| US07/024,452 US4741757A (en) | 1986-04-10 | 1987-03-11 | Thiophenesulfonamides |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/849,332 Division US4668281A (en) | 1985-05-20 | 1986-04-10 | Thiophenesulfonamides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4741757A true US4741757A (en) | 1988-05-03 |
Family
ID=25305578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/024,452 Expired - Fee Related US4741757A (en) | 1986-04-10 | 1987-03-11 | Thiophenesulfonamides |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4741757A (en) |
| JP (1) | JPS62242678A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6887831B1 (en) | 1999-08-06 | 2005-05-03 | Bayer Aktiengesellschaft | Substituted thienyl(amino)sulfonylureas |
| US6964939B1 (en) | 1999-07-15 | 2005-11-15 | Bayer Aktiengesellschaft | Substituted thiene-3-yl-sulfonyl amino(thio)carbonyl-triazolin(thi)ones |
| US20080020932A1 (en) * | 2004-03-05 | 2008-01-24 | Bayer Cropscience Ag | Method for Combating Weeds |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501607A (en) * | 1978-09-27 | 1985-02-26 | E. I. Du Pont De Nemours And Company | Herbicidal triazine sulfonamides |
| US4515626A (en) * | 1982-10-06 | 1985-05-07 | Ciba Geigy Corporation | N-(Cyclopropyl-triazinyl-n'-(arylsulfonyl) ureas having herbicidal activity |
| US4547217A (en) * | 1982-02-08 | 1985-10-15 | E. I. Du Pont De Nemours And Company | Thiophene or furan herbicides |
| US4589909A (en) * | 1984-06-05 | 1986-05-20 | E. I. Du Pont De Nemours And Company | Benzofuran and benzothiophene sulfonamides |
-
1986
- 1986-08-20 JP JP61192979A patent/JPS62242678A/en active Pending
-
1987
- 1987-03-11 US US07/024,452 patent/US4741757A/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501607A (en) * | 1978-09-27 | 1985-02-26 | E. I. Du Pont De Nemours And Company | Herbicidal triazine sulfonamides |
| US4547217A (en) * | 1982-02-08 | 1985-10-15 | E. I. Du Pont De Nemours And Company | Thiophene or furan herbicides |
| US4515626A (en) * | 1982-10-06 | 1985-05-07 | Ciba Geigy Corporation | N-(Cyclopropyl-triazinyl-n'-(arylsulfonyl) ureas having herbicidal activity |
| US4589909A (en) * | 1984-06-05 | 1986-05-20 | E. I. Du Pont De Nemours And Company | Benzofuran and benzothiophene sulfonamides |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6964939B1 (en) | 1999-07-15 | 2005-11-15 | Bayer Aktiengesellschaft | Substituted thiene-3-yl-sulfonyl amino(thio)carbonyl-triazolin(thi)ones |
| US7642221B2 (en) | 1999-07-15 | 2010-01-05 | Bayer Aktiengesellschaft | Substituted thien-3-yl-sulphonylamino(thio)carbonyl-triazoline(ethi)ones |
| US20100056798A1 (en) * | 1999-07-15 | 2010-03-04 | Bayer Cropscience Ag | Substituted thien-3-yl-sulphonylamino(thio)carbonyl-triazolin(ethi)ones |
| US7858805B2 (en) | 1999-07-15 | 2010-12-28 | Bayer Aktiengesellschaft | Substituted thien-3-yl-sulphonylamino(thio)carbonyl-triazolin(ethi)ones |
| US6887831B1 (en) | 1999-08-06 | 2005-05-03 | Bayer Aktiengesellschaft | Substituted thienyl(amino)sulfonylureas |
| US7091158B2 (en) | 1999-08-06 | 2006-08-15 | Bayer Aktiengesellschaft | Substituted thienyl(amino)sulphonylureas |
| US20080020932A1 (en) * | 2004-03-05 | 2008-01-24 | Bayer Cropscience Ag | Method for Combating Weeds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62242678A (en) | 1987-10-23 |
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